CN110314535A - A kind of micro-nano bubble coupling FexThe system and method for S absorption flue gas - Google Patents
A kind of micro-nano bubble coupling FexThe system and method for S absorption flue gas Download PDFInfo
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- CN110314535A CN110314535A CN201910532114.3A CN201910532114A CN110314535A CN 110314535 A CN110314535 A CN 110314535A CN 201910532114 A CN201910532114 A CN 201910532114A CN 110314535 A CN110314535 A CN 110314535A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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Abstract
The present invention relates to a kind of micro-nano bubbles to couple FexThe system and method for S absorption flue gas.The system includes: SO2Bottle (1), NO bottles (2), air bottle (3) is connected with gas buffer bottle (5) respectively, gas buffer bottle (5), water tank (7) are connect with micro-nano bubble generator (6) respectively, and micro-nano bubble generator (6) connect with reactive absorption tower (10) bottom end.This method comprises: with NO, SO2Gas source with the mixed gas of air as micro-nano bubble, configuration contain FexThe solution of S is implemented to absorb the catalysis oxidation of NO under normal temperature and pressure conditions as absorbing liquid.The catalyst that this method uses is the Fe in slagxS has that catalyst comprehensive utilization ratio is high, device is simple, denitration efficiency is high and the excellent properties such as absorbing liquid recoverable, has a good application prospect and industrialization potential in environmental technology field.
Description
Technical field
The invention belongs to wet absorption denitrating system and method field, in particular to a kind of micro-nano bubble couples FexS inhales
Receive the system and method for flue gas.
Background technique
In sintering flue gas, NO accounts for NOx95% and be insoluble in water and alkaline solution, SO2It is soluble easily in water, it is relatively easy to remove,
So NO can be oxidized to NO with oxidant2, NO2Solubility is higher in water, is easy to be absorbed, and reaches removing NOxEffect
Fruit.The wet absorption desulphurization denitration of advanced oxidation coupling at present becomes research hotspot, i.e., NO is oxidized to NO in the solution2And molten
It is absorbed in liquid.Existing research utilizes oxidant such as O more3、ClO2And strong electric discharge generates hydroxyl radical free radical (OH) and aoxidizes NO, SO2,
Obtain higher removal efficiency.But these technology oxidant consumptions are excessive, at high cost, therefore explore and replaced using metal waste
Oxidant, which carries out desulphurization denitration, has good realistic meaning.
Micro-nano bubble refers to bubble of the diameter between tens μm to several hundred nm.It, can be with currently, according to production principle
Micro-nano bubble production method is divided into supercritical ultrasonics technology, shearing air method, pressurization decompression method and electrolysis deposition method etc..It is micro-nano
Bubble has the characteristics that the residence time is long in water, interface zeta potential is high, mass-transfer efficiency is high, can generate hydroxyl radical free radical, in recent years,
The great attention of researcher all over the world is caused, research achieves perhaps in industries such as medical treatment, agricultural, aquacultures
Mostly breakthrough progress.Also gradually increase in the research of environmental area with application.Research shows that Fe2+Addition, can be improved
Effectively improve the absorption efficiency of NO；And guarantee SO2Completely remove.
FexS is to obtain slag containing golden troilite matte smelting, is the residue after the valuable metals such as melting Au, sulfonium iron
Conjunction object waste residue environmental pollution is serious, cost recovery is high.In FeSxIn the application of the similar substance of chemical composition, FeS is one
Generally existing non-toxic mineral, the applicating history in relation to FeS in soil and water remediation can trace back to for 20th century 90 years
Generation.FexIron content is high in S, has instead of Fe2+Make the possibility of catalyst, accordingly, it is considered to design with FexS is catalyst, coupling
Micro-nano bubble is closed, catalysis oxidation absorbs the system of NO in flue gas, and thinks that it has a good application prospect.
Water, air and NO are mixed and are generated micro-nano bubble by the characteristics of Jiang, sunlight brightness et al. are using micro-nano bubble
For the absorption of NO, optimum condition achieves 69.18% assimilation effect.However a large amount of Fe is added in its research2+, can make
At the secondary pollution of water body.Therefore the present invention uses the Fe that can be recycledxS replaces Fe2+, not only saved cost, additionally it is possible to
Secondary pollution is avoided, the NO in efficient process flue gas is reachedxAnd SO2。
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of micro-nano bubbles to couple FexS absorb flue gas system and
Method.To overcome the defects of advanced oxidation coupling wet absorption denitration is excessive at oxidant consumption, at high cost in the prior art.
The present invention provides a kind of micro-nano bubbles to couple FexThe system that S absorbs flue gas, the system comprises: SO2Bottle, NO
Bottle, air bottle are connected with gas buffer bottle respectively, and gas buffer bottle, water tank are connect with micro-nano bubble generator respectively, micro-nano
Rice bubble generator is connect with reactive absorption tower bottom end；The reactive absorption tower, which is equipped with, contains FexThe absorbing liquid of S particle.
The system also includes tail gas absorber, ion chromatograph, flue gas analyzer and blenders；The tail gas absorber
It is connect with reactive absorption tower top end, the ion chromatograph is connect with reactive absorption tower, and the flue gas analyzer is connected to gas
Between surge flask and micro-nano bubble generator, the blender is arranged in reactive absorption tower.
The SO2Bottle, NO bottles, air bottle passes through gas flowmeter respectively and is connected with gas buffer bottle.
The water capacity of the reactive absorption tower is 200L.
The reagent is bought by traditional Chinese medicines, FexS particle source is certain factories and miness slag.
The present invention also provides a kind of micro-nano bubbles to couple FexThe method of S absorption flue gas, comprising:
(1) Fe is added in tap waterxObtained absorbing liquid is passed through reactive absorption tower, wherein Fe by S particlexS particle with
The ratio of tap water is 1-20g:100-150L；
(2) by SO2SO in bottle2, NO in NO bottles, air each leads into gas buffer bottle and mixes in air bottle, simulate cigarette
Then gas injects reactive absorption tower in the micro-nano bubble generator of obtained gaseous mixture entrance synchronous with tap water in water tank,
Micro-nano Gas-Liquid Dispersion system is formed, is stirred in reactive absorption tower, catalysis oxidation absorbs.
Fe in the step (1)xS grain diameter is 40-400 mesh, may be, for example, 40~60 mesh, 60~80 mesh, 80~200
200~300 mesh of mesh, 300~400 mesh, preferably 200~300 mesh.
NaCl, NaCl concentration 0.1-0.9g/L are added in absorbing liquid in the step (1).
The NaCl concentration is 0.1g/L, 0.3g/L, 0.5g/L, 0.7g/L or 0.9g/L, preferably 0.3g/L.
Absorption liquid pH is 3-11 in the step (1).
The pH is 3,5,7,9,11, preferably 5.
Originally water volume is 125L, Fe in the step (1)xS particle dosage be 1g, 5g, 10g, 15g or 20g, preferably
For 20g.
The specified flow of inlet water of micro-nano bubble generator (6) is 10L/min in the step (2), and specified air inflow is
2L/min。
The concentration of NO is 1600-6700mg/m in gaseous mixture in the step (2)3, SO2Concentration be 5000-6700mg/
m3。
The air inflow is measured by German Seitron C600 type flue gas analyzer.
Tail gas is absorbed by tail gas absorber (11) in reactive absorption tower (10) in the step (2).
Absorbing liquid Nitrite, nitrate radical content are surveyed by ion chromatography after catalysis oxidation absorbs in the step (2)
It is fixed, and NO absorption efficiency is calculated with this.
NO calculation method of absorption efficiency of the present invention:
In formula (1): c1NO in absorbing liquid3 -And NO2 -The mass concentration of (in terms of N), mgL-1；q1For flow of inlet water, L
min-1；T is system operation time, min；m1For the quality of air inlet NO (in terms of N).
In formula (2): ρnFor the mass concentration of NO, mgL-1；P1For the pressure after gas decompression, Pa；P0For atmospheric pressure, Pa；
q2For gas flow, mLmin-1；T is system operation time.
Fe of the present inventionxS catalysis oxidation principle of absorption:
Fe in the present inventionxS has catalytic action, and micro-nano bubble has residence time length, increase gas-liquid mass transfer in water
The features such as generating hydroxyl radical free radical when efficiency, large specific surface area and rupture.Specifically, the present invention is with NO and SO2Mixing
Gas source of the gas as micro-nano bubble, configuration contain FexThe solution of S is implemented under normal temperature and pressure conditions as absorbing liquid to NO
Catalysis oxidation absorb.
In conclusion the micro-nano bubble of the present invention couples FexThe S catalysis oxidation and oxidative absorption for absorbing NO in flue gas has
Good operability.Micro-nano bubble is injected to water high speed by micro-nano bubble generator, in water micro-nano bubble
A variety of oxygen radicals (active oxygen anion, hydrogen ion, hydroxide ion, hydroxyl ion, water oxygen base ion, water are generated in space
Close electronics etc.), in conjunction with FexThe catalytic action of S obtains superpower oxidation effectiveness.
Beneficial effect
(1) Fe of the present inventionxS reaction front and back will not cause water body as catalyst secondary without apparent object phase change
Pollution can be used as the material of good catalytic oxidation NO removing；
(2) final absorbing liquid is the nitric acid solution of higher concentration, and implementable recycling does not generate secondary pollution；
(3) simple process, device composition is simple, and low energy consumption is easily operated.
Detailed description of the invention
Fig. 1 is the micro-nano bubble coupling Fe of the present inventionxThe system structure diagram of S absorption flue gas.
Fig. 2 is Fe in embodiment 1xScanning electron microscope (SEM) photograph before and after S particle reaction.
Fig. 3 is Fe in embodiment 1xXRD spectrum before and after S particle reaction.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The present embodiment provides a kind of micro-nano bubbles to couple FexThe system of S absorption flue gas, comprising: SO2Bottle 1, NO bottle 2, sky
Gas cylinder 3 is connected by gas flowmeter 4 with gas buffer bottle 5 respectively, and gas buffer bottle 5, water tank 7 are sent out with micro-nano bubble respectively
Raw device 6 connects, and micro-nano bubble generator 6 is connect with 10 bottom end of reactive absorption tower；Reactive absorption tower 10, which is equipped with, contains FexS particle
Absorbing liquid；Tail gas absorber 11 is connect with 10 top of reactive absorption tower, and ion chromatograph 12 is connect with reactive absorption tower 10, cigarette
Gas analyzer 8 is connected between gas buffer bottle 5 and micro-nano bubble generator 6, and blender 9 is arranged in reactive absorption tower 10
It is interior.
The present embodiment also provides a kind of micro-nano bubble coupling FexThe method that S absorbs flue gas, specifically:
(1) Fe that 10g partial size is 300~400 mesh is added in 150L tap waterxS particle, the pH for adjusting absorbing liquid is 7,
Then pass to reactive absorption tower 10；
(2) by SO2SO in bottle 12, NO in NO bottle 2, air each leads into gas buffer bottle 5 and mixes in air bottle 3, control
NO concentration is 6700mg/m3, SO2Concentration is 6700mg/m3, obtained gaseous mixture is synchronous with distilled water in water tank 7 into micro-nano
In rice bubble generator 6, the specified flow of inlet water of micro-nano bubble generator 6 is 10L/min, and specified air inflow is 2L/min, so
Reactive absorption tower 10 (water capacity 200L) is injected afterwards, micro-nano Gas-Liquid Dispersion system is formed in reactive absorption tower 10, anti-
Mechanical stirring in absorption tower 10 is answered, Fe is madexS even particulate dispersion realizes the sufficiently catalytic oxidation and absorption of NO.
(3) absorbing liquid Nitrite, nitrate radical content calculate NO absorption efficiency by ion chromatography with this.
Remaining flue gas is absorbed by tail gas absorber.NO oxidative absorption efficiency has reached 88.3%, SO2Oxidative absorption efficiency reaches
100%.
Fig. 1 shows: Fe in the present embodimentxS particle is irregular shape, and the surface topography before and after use has apparent poor
It is different.It is relatively flat closely knit using front surface；Become coarse using rear surface, this is because FexThe substance on the surface S takes part in NO's
Caused by oxidative absorption process.
Fig. 2 shows: Fe before and after usexThere is no variation, the only Fe after use for the characteristic peak positions of SxS diffraction peak intensity
Degree weakens, and illustrates FexThe object of S does not change mutually in the reaction.
Embodiment 2
The present embodiment provides a kind of micro-nano bubbles to couple FexS absorbs the system and method for flue gas, and addition 5g partial size is
The Fe of 300~400 meshxS particle, and add NaCl, makes NaCl concentration 0.5g/L in absorbing liquid, pH 5, remaining with implementation
Example 1 is identical.NO oxidative absorption efficiency has reached 95.3%, SO2Oxidative absorption efficiency has reached 100%.
Embodiment 3
The present embodiment provides a kind of micro-nano bubbles to couple FexS absorbs the system and method for flue gas, and addition 5g partial size is
The Fe of 300~400 meshxS particle, NO concentration are 1674mg/m3, remaining is same as Example 1.NO oxidative absorption efficiency reaches
99.26%, SO2Oxidative absorption efficiency has reached 100%.
Comparative example 1
Chinese patent CN108355483A disclose a kind of system based on the micro-nano bubble wet denitration of ozone coupling and
Method, what which used is Fe containing oxygen transfer catalyst2+Or Mn2+Ion, preparation NO volumetric concentration are 6700mg/m3Mixing
Gas, [O in mixed gas3]/[NO] be 0.5；NaCl mass concentration is 0.5g/L, uses MnSO4·4H2O prepares 2mmol/L's
Absorbing liquid 40L removes NO using ozone and micro-nano bubble, and removal efficiency reaches 92.3%.But there are gases, and single, ionic is urged
Agent can not recycle, absorbing liquid secondary pollution problems.
For the present invention compared with Chinese patent CN108355483A, the present invention under the same conditions, uses FexS replaces Mn2+, can
So that SO2The absorption efficiency that absorptivity reaches 100%, NO reaches 95.3%.In addition, the present invention is to NO and SO2Mixed gas is simultaneously
It is handled, absorbs SO in catalysis oxidation2While complete to the oxidative absorption of NO, constituent more be bonded practical flue gas, reality
Integration desulfurization denitration is showed.The present invention replaces ozone using air, has saved cost to a certain extent, has simplified system.
Use FexS slag can recycle realization and recycle as oxygen transfer catalyst, and achieve the purpose that waste recycling.
Claims (7)
1. a kind of micro-nano bubble couples FexThe system of S absorption flue gas, which is characterized in that the system comprises: SO2Bottle (1), NO
Bottle (2), air bottle (3) are connected with gas buffer bottle (5) respectively, gas buffer bottle (5), water tank (7) respectively with micro-nano bubble
Generator (6) connection, micro-nano bubble generator (6) connect with reactive absorption tower (10) bottom end；The reactive absorption tower (10)
Equipped with containing FexThe absorbing liquid of S particle.
2. system according to claim 1, which is characterized in that the system also includes tail gas absorbers (11), ion chromatography
Instrument (12), flue gas analyzer (8) and blender (9)；The tail gas absorber (11) connect with reactive absorption tower (10) top, institute
It states ion chromatograph (12) to connect with reactive absorption tower (10), the flue gas analyzer (8) is connected to gas buffer bottle (5) and micro-
Between nano-bubble generator (6), blender (9) setting is in reactive absorption tower (10).
3. a kind of micro-nano bubble couples FexThe method of S absorption flue gas, comprising:
(1) Fe is added in tap waterxObtained absorbing liquid is passed through reactive absorption tower (10), wherein Fe by S particlexS particle with
The ratio of tap water is 1-20g:100-150L；
(2) by SO2SO in bottle (1)2, NO in NO bottles (2), air each leads into mixing in gas buffer bottle (5) in air bottle (3),
By in obtained gaseous mixture entrance micro-nano bubble generator (6) synchronous with tap water in water tank (7), reactive absorption is then injected
Tower (10), the stirring in reactive absorption tower (10), catalysis oxidation absorb.
4. method according to claim 3, which is characterized in that Fe in the step (1)xS grain diameter is 40-400 mesh；It inhales
It receives in liquid and adds NaCl, NaCl concentration 0.1-0.9g/L；Absorption liquid pH is 3-11.
5. method according to claim 3, which is characterized in that micro-nano bubble generator (6) is specified in the step (2)
Flow of inlet water is 10L/min, and specified air inflow is 2L/min.
6. method according to claim 3, which is characterized in that the concentration of NO is 1600- in gaseous mixture in the step (2)
6700mg/m3, SO2Concentration be 5000-6700mg/m3。
7. method according to claim 3, which is characterized in that in the step (2) in reactive absorption tower (10) tail gas by tail
Aspiration tower (11) absorbs.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112044443A (en) * | 2020-09-16 | 2020-12-08 | 东华大学 | Micro-nano bubble catalyst and preparation method and application thereof |
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| CN108404616A (en) * | 2018-02-02 | 2018-08-17 | 东华大学 | A kind of wet denitration system and method absorbing flue gas based on ozone oxidation |
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2019
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| US9757687B2 (en) * | 2012-01-09 | 2017-09-12 | Alloys Cleaning, Inc. | Removal of atmospheric pollutants from gas, related apparatus, processes and uses thereof |
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| CN108355483A (en) * | 2018-02-02 | 2018-08-03 | 东华大学 | A kind of wet denitration system and method absorbing flue gas based on catalytic ozonation |
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| CN112044443A (en) * | 2020-09-16 | 2020-12-08 | 东华大学 | Micro-nano bubble catalyst and preparation method and application thereof |
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